PHENOL

Phenol,

also

compound with

known
the

as carbolic

acid,

is

an aromatic organic

molecular formula C6H5OH.

It

is

white crystalline solid that is volatile. The molecule consists of a phenyl

group (C6H5)

bonded

to

a hydroxyl

group (OH).

It

is

mildly acidic and requires careful handling due to its propensity to

cause chemical burns.
Phenol was first extracted from coal tar, but today is produced on a large
scale (about 7 billion kg/year) from petroleum. It is an important
industrial commodity as a precursor to many materials and useful
compounds. It is primarily used to synthesize plastics and related
materials. Phenol and its chemical derivatives are essential for
production
of polycarbonates, epoxies, Bakelite, nylon, detergents, herbicides such
as phenoxy herbicides, and numerous pharmaceutical drugs.

PROPERTIES
Phenol is an organic compound. Phenol is appreciably soluble in water,
with about 84.2 g dissolving in 1000 mL (0.895 M). Homogeneous
mixtures of phenol and water at phenol to water mass ratios of ~2.6 and
higher are possible. The sodium salt of phenol, sodium phenoxide, is far
more water-soluble.
Acidity
Phenol

is

weakly

acidic

and

at

high

pHs

gives

the phenolate anion C6H5O (also called phenoxide):

PhOH PhO + H+

(K = 1010)

Compared to aliphatic alcohols, phenol is about 1 million times more

acidic, although it is still considered a weak acid. It reacts completely
with aqueous NaOH to lose H+, whereas most alcohols react only
partially.
One explanation for the increased acidity over alcohols is resonance
stabilization of the phenoxide anion by the aromatic ring. In this way,
the

negative

charge

on

oxygen

is

delocalized

on

to

the ortho and para carbon atoms. In another explanation, increased

acidity is the result of orbital overlap between the oxygen's lone pairs
and the aromatic system. In a third, the dominant effect is
the induction from the sp2hybridised carbons; the comparatively more
powerful inductive withdrawal of electron density that is provided by
the sp2 system compared to an sp3 system allows for great stabilization
of the oxyanion.
The pKa of

the enol of acetone is

10.9,

comparable

to

that

for

phenol. The acidities of phenol and acetone enol diverge in the gas

phase owing to the effects of solvation. About 13 of the increased acidity

of phenol is attributable to inductive effects, with resonance accounting
for the remaining difference.
Phenoxide anion

Resonance structures of the phenoxide anion

The phenoxide anion has a similar nucleophilicity to free amines, with
the further advantage that its conjugate acid (neutral phenol) does not
become entirely deactivated as a nucleophile even in moderately acidic
conditions. Phenolate esters are more stable toward hydrolysis than acid
anhydrides and acyl halides but are sufficiently reactive under mild
conditions to facilitate the formation of amide bonds.
Tautomerism

Phenol-cyclohexadienone tautomerism
Phenol exhibits keto-enol tautomerism with its unstable keto tautomer
cyclohexadienone, but only a tiny fraction of phenol exists as the keto
form. The equilibrium constant for enolisation is approximately 10 13,
meaning that only one in every ten trillion molecules is in the keto form
at any moment. The small amount of stabilisation gained by exchanging
a C=C bond for a C=O bond is more than offset by the large
destabilisation resulting from the loss of aromaticity. Phenol therefore
exists essentially entirely in the enol form.

Phenoxides

are enolates stabilised

by aromaticity.

Under

normal

circumstances, phenoxide is more reactive at the oxygen position, but

the oxygen position is a "hard" nucleophile whereas the alpha-carbon
positions tend to be "soft".
Reactions
Phenol is highly reactive toward electrophilic aromatic substitution as
the oxygen atom's pi electrons donate electron density into the ring. By
this general approach, many groups can be appended to the ring,
via halogenation, acylation, sulfonation, and other processes. However,
phenol's ring is so strongly activatedsecond only to anilinethat
bromination or chlorination of phenol leads to substitution on all carbon
atoms ortho and para to the hydroxy group, not only on one carbon.
Phenol reacts with dilute nitric acid at room temperature to give a
mixture of 2-nitrophenol and 4-nitrophenol while with concentrated
nitric acid, more nitro groups get substituted on the ring to give 2,4,6trinitrophenol which is known as picric acid.
Aqueous solutions of phenol are weakly acidic and turn blue litmus
slightly

to

red.

Phenol

is

easily

neutralized

by sodium

hydroxide forming sodium phenate or phenolate, but being weaker

than carbonic

acid,

it

cannot

be

neutralized

by sodium

bicarbonate or sodium carbonate to liberate carbon dioxide.

C6H5OH + NaOH C6H5ONa + H2O
When a mixture of phenol and benzoyl chloride are shaken in presence
of dilute sodium hydroxide solution, phenyl benzoate is formed. This is
an example of the Schotten-Baumann reaction:
C6H5OH + C6H5COCl C6H5OCOC6H5 + HCl

Phenol is reduced to benzene when it is distilled with zinc dust. The

same when phenol vapour is passed over granules of zinc at 400 C:
C6H5OH + Zn C6H6 + ZnO
When phenol is reacted with diazomethane in the presence of boron
trifluoride (BF3), anisole is obtained as the main product and nitrogen
gas as a byproduct.
C6H5OH + CH2N2 C6H5OCH3 + N2
When phenol reacts with iron(III) chloride solution, an intense violetpurple solution is formed.

PRODUCTION
Because of phenol's commercial importance, many methods have been
developed for its production. The dominant current route, accounting for
95% of production (2003), is the cumene process, which involves the
partial oxidation of cumene (isopropylbenzene)

via

the

Hock

rearrangement:
C6H5CH(CH3)2 + O2 C6H5OH + (CH3)2CO
Acetone is produced as a by-product. Compared to most other
processes, the cumene process uses relatively mild synthesis conditions,
and relatively inexpensive raw materials. However, to operate
economically, there must be demand for both phenol, and the acetone
by-product.In 2010, worldwide demand for acetone was approximately
6.7 million tonnes, 83 percent of which was satisfied with acetone
produced by the cumene process.
An early commercial route, developed by Bayer and Monsanto in the
early

1900s,

begins

with benzenesulfonate:

with

the

reaction

of

strong

base

C6H5SO3H + 2 NaOH C6H5OH + Na2SO3 + H2O

Other methods under consideration involve:
hydrolysis of chlorobenzene, using base (Dow's Process) or steam
(RaschigHooker process):
C6H5Cl + H2O C6H5OH + HCl
direct oxidation of benzene with nitrous oxide, a potentially
"green" process:
C6H6 + N2O C6H5OH + N2
oxidation of toluene, as developed by Dow Chemical:
C6H5CH3 + 2 O2 C6H5OH + CO2 + H2O
In the Lummus Process, the oxidation of toluene to benzoic acid is
conducted separately.
Phenol is also a recoverable byproduct of coal pyrolysis.

USES
The major uses of phenol, consuming two thirds of its production,
involve its conversion to precursors for plastics. Condensation with
acetone

gives bisphenol-A,

to polycarbonates and epoxide resins.

key

Condensation

precursor
of

phenol,

alkylphenols, or diphenols with formaldehyde gives phenolic resins, a

famous example of which is Bakelite. Partial hydrogenation of phenol
gives cyclohexanone, a precursor to nylon. Nonionic detergents are
produced

by

alkylation

of

phenol

to

give

the alkylphenols,

e.g., nonylphenol, which are then subjected to ethoxylation.

Phenol is also a versatile precursor to a large collection of drugs, most
notably aspirin but also many herbicides and pharmaceutical drugs.
Phenol is also used as an oral anesthetic/analgesic in products such

as Chloraseptic or other brand name and generic equivalents, commonly

used to temporarily treat pharyngitis.
Phenol

is

component

in liquid/liquid phenolchloroform

extraction technique used in molecular biology for obtaining nucleic

acids from tissues or cell culture samples. Depending on the pH of the
solution either DNA or RNA can be extracted.
Niche uses
Phenol is so inexpensive that it attracts many small-scale uses. It once
was widely used as an antiseptic, especially as carbolic soap, from the
early 1900s to the 1970s. It is a component of industrial paint
strippers used in the aviation industry for the removal of epoxy,
polyurethane and other chemically resistant coatings.
Phenol

derivatives

are

also

of cosmetics including sunscreens, hair

used

in

the

preparation

colorings,

and skin

lightening preparations.
Concentrated phenol liquids are commonly used for permanent
treatment of ingrown toe and finger nails, a procedure known as a
chemical matrixectomy. The procedure was first described by Otto Boll
in 1945. Since that time it has become the chemical of choice for
chemical matrixectomies performed by podiatrists.
Phenol spray is used medically to help sore throat.
Phenol is the active ingredient in some oral analgesics such
as Chloraseptic spray and Carmex.

NATURAL OCCURRENCES
Phenol is a normal metabolic product, excreted in quantities up to
40 mg/L in human urine.

The temporal gland secretion of male elephants showed the presence of

phenol and 4-methylphenol during musth.
It is also one of the chemical compounds found in castoreum. This
compound is gathered from the plants the beaver eats.
Occurrence in whisky
Phenol is a measurable component in the aroma and taste of the
distinctive Islay scotch whisky, generally ~30 ppm, but it can be over
160ppm in the malted barley used to produce whisky. This amount is
different from and presumably higher than the amount in the distillate.

BIODEGRADATION
Cryptanaerobacter

phenolicus is

bacterium

species

that

produces benzoate from phenol via 4-hydroxybenzoate. Rhodococcus

phenolicus is a bacterium species able to degrade phenol as sole carbon
sources.

TOXICITY
Phenol and its vapors are corrosive to the eyes, the skin, and the
respiratory tract. Its corrosive effect on skin and mucous membranes is
due to a protein-degenerating effect. Repeated or prolonged skin contact
with phenol may cause dermatitis, or even second and third-degree
burns. Inhalation of phenol vapor may cause lung edema. The substance
may cause harmful effects on the central nervous system and heart,
resulting

in dysrhythmia, seizures,

and coma. The kidneys may

be

affected as well. Long-term or repeated exposure of the substance may

have harmful effects on the liver and kidneys. There is no evidence that
phenol

causes cancer in

humans. Besides

its hydrophobic effects,

another mechanism for the toxicity of phenol may be the formation

of phenoxyl radicals.
Since phenol is absorbed through the skin relatively quickly, systemic
poisoning can occur in addition to the local caustic burns. Resorptive
poisoning by a large quantity of phenol can occur even with only a small
area of skin, rapidly leading to paralysis of the central nervous system
and a severe drop in body temperature. The LD for oral toxicity is less
than 0.5 mg/kg for dogs, rabbits, or mice; the minimum lethal human
dose was cited as 140 mg/kg. The Agency for Toxic Substances and
Disease Registry (ATSDR), U.S. Department of Health and Human
Services states the fatal dose for ingestion of phenol is from 1 to 32 g.
Chemical burns from skin exposures can be decontaminated by washing
with polyethylene glycol, isopropyl alcohol, or perhaps even copious
amounts of water. Removal of contaminated clothing is required, as well
as immediate hospital treatment for large splashes. This is particularly
important if the phenol is mixed with chloroform (a commonly used
mixture in molecular biology for DNA and RNA purification). Phenol is
also a reproductive toxin causing increased risk of abortion and low
birth weight indicating retarded development in utero.

PHENOLS
The word phenol is also used to refer to any compound that contains a
six-membered aromatic ring, bonded directly to a hydroxyl group (OH). Thus, phenols are a class of organic compounds of which the
phenol discussed in this article is the simplest member.